Dynamic properties of methyl(trimethylphosphane)nickel complexes containing (2-diphenylphosphanyl)phenylamido ligands

Article abstract of DOI:10.1002/ejic.200390031

P,N-chelates of nickel NiCl[2-(Ph₂P)C₆H₄NR](PMe₃) (1: R = H; 2: R = SiMe₃) have been obtained from NiCl₂(PMe₃)₂ and 2-(Ph₂P)C₆H₄NRLi. Reaction with MeLi affords methylnickel compounds NiMe[2-(Ph₂P)C₆H₄NR](PMe₃) (3: R = H; 4: R = Me; 5: R = SiMe₃). By the same route NiMe[2- (R¹R²P)C₆H₄NR](PMe₃) (6: R¹ = R² = CHMe₂) was synthesized. Solutions in THF contain cis and trans isomers of square-planar complexes, and dynamic NMR spectroscopy shows dissociation of trimethylphosphane to be more rapid in the trans isomers. In a crystal of 5 the molecular structure is cis-5. Out of these complexes only 3 and 4 add trimethylphosphane to form pentacoordinate compounds NiMe[2- (Ph₂P)C₆H₄NR](PMe₃)₂ (7, 8) in the crystal as shown by the molecular structure of 7 while in THF equilibria 7 ? cis-1 and 8 ? cis-2 are observed by NMR spectroscopy. The same solution properties are found with NiMe[2- (R¹R²P)C₆H₄NR] (PMe₃)₂ (9: R¹ = CMe₃, R² = Ph). Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2003.

Full text of DOI:10.1002/ejic.200390031

FULL PAPER
Dynamic Properties of Methyl(trimethylphosphane)nickel Complexes
Containing (2-Diphenylphosphanyl)phenylamido Ligands
Hans-Friedrich Klein,*[a] Robert Beck,[a] and Olaf Hetche[a]
Keywords: Solution dynamics / Nickel / Coordination numbers 4 and 5 / Structure elucidation
P,N-chelates of nickel NiCl[2-(Ph2P)C6H4NR](PMe3) (1: R =
H; 2: R = SiMe3) have been obtained from NiCl2(PMe3)2 and
2-(Ph2P)C6H4NRLi. Reaction with MeLi affords methylnickel
compounds NiMe[2-(Ph2P)C6H4NR](PMe3) (3: R = H; 4: R =
is cis-5. Out of these complexes only 3 and 4 add trimethyl-
phosphane to form pentacoordinate compounds NiMe[2-
(Ph2P)C6H4NR](PMe3)2 (7, 8) in the crystal as shown by the
molecular structure of 7 while in THF equilibria 7 Ǟǟ cis-1 and
Ǟ
Me; 5:
R
=
SiMe3). By the same route NiMe[2-
8
cis-2 are observed by NMR spectroscopy. The same
ǟ
(R1R2P)C6H4NR](PMe3) (6: R1 = R2 = CHMe2) was synthe-
solution
properties
are
found
with
NiMe[2-
sized. Solutions in THF contain cis and trans isomers of (R1R2P)C6H4NR](PMe3)2 (9: R1 = CMe3, R2 = Ph).
square-planar complexes, and dynamic NMR spectroscopy
shows dissociation of trimethylphosphane to be more rapid
( Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim,
in the trans isomers. In a crystal of 5 the molecular structure Germany, 2003)
Introduction
nickel() with added Et2AlCl turns out to be a catalyst in
the oligomerization of propene as described by Corain et
al.[3]. As a model of a growing alkylmetal chain we have
synthesized some methylnickel complexes containing P,N-
chelating and trimethylphosphane ligands and report here
on molecular structures and dynamic properties in solution.
A well-known strategy to avoid a bridging coordination
mode in transition metal amides is the use of chelating li-
gands. As a convenient anchoring group the 2-(diphenyl-
phosphanyl) group induces P,N-chelating systems to form
five-membered metallacyles. Usually these are derived from
2-(diphenylphosphanyl)aniline which is isoelectronic with
P,O-chelating 2-(diphenylphosphanyl)phenol and because
of its potential in homogeneous catalysis of olefin reactions
merits further investigation. 2-(Diphenylphosphanyl)aniline
has been shown by Cooper et al.[1] to form mononuclear
bis(chelate) compounds of platinum and nickel acting either
as a neutral or as an anionic 4-electron donor (Scheme 1).
Results and Discussion
N-Lithiated 2-(diphenylphosphanyl)anilines react with
trans-NiCl2(PMe3)2 [Equation (1)] to afford the chloro-
nickel complexes 1 and 2 as green solids which are sparingly
soluble in pentane or ether.
(1)
Scheme 1. Square-planar bis(P,N-chelates)
The 31P NMR spectrum obtained from a THF solution
of 1 or 2 at 233 K shows four doublet resonances. The pair
containing the large P,P coupling is assigned to trans-1
(62%) and trans-2 (66%), while the pair showing the small
P,P coupling is due to cis-1 (38%) and cis-2 (34%), respect-
ively. Similar mixtures of isomers have been observed with
related cationic palladium complexes.[4]
2-(Diphenylphosphanyl)-N-methylanilido compounds of
rhodium() and iridium() have been investigated by Dahl-
enburg et al.,[2] while 2-(diphenylphosphanyl)-N,N-di-
methylaniline in penta- and tetracoordinate complexes of
[a]
Eduard-Zintl-Institut für Anorganische and Physikalische
Chemie der Technischen Universität Darmstadt,
Petersenstrasse 18, 64285 Darmstadt, Germany
Added trimethylphosphane accelerates the exchange of
ligands but does not alter the green color of these solutions
232
 2003 WILEY-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim 1434Ϫ1948/03/0102Ϫ0232 $ 20.00ϩ.50/0 Eur. J. Inorg. Chem. 2003, 232Ϫ239

Dynamic Properties of Methyl(trimethylphosphane)nickel Complexes
FULL PAPER
and thereby indicates the absence of a pentacoordinate
compound. Addition of a second mol-equiv. of LiMe or use
of trans-NiMeCl(PMe3)2 as a reactant [Equation (2)] fur-
nishes the corresponding methylnickel compounds.
(3)
The 31P NMR spectra in THF show a large coordination
chemical shift of the chelate-P nucleus by 52 ppm to low
field and a resonance for the coordinated trimethylphos-
phane ligand at δ ഠ Ϫ2 ppm. Surprisingly, the cis and trans
isomers show different behavior at variable temperatures.
Only the cis isomers continue to display a doublet of doub-
lets (2JP,P ഠ 30 Hz) between 298 and 213 K (Figure 1) while
the large trans coupling (2JP,P ഠ 300 Hz) is attained in the
low-temperature limit. Upon warming, both doublet reson-
ances of trans-3Ϫ6 collapse to singlets caused by incipient
dissociation of trimethylphosphane. Therefore, the slightly
shifted broad singlet at δ ϭ Ϫ5 ppm (298 K) must be re-
garded as an average of rapidly exchanging free and coord-
inated trimethylphosphane which also involves the penta-
coordinate species (see below).
Single crystals of 5 obtained from pentane when subject
to an X-ray diffraction experiment were shown to consist
of cis-5 (Figure 2). The unit cell contains two molecules that
differ mainly in the rotational position of a phenyl substitu-
ent. The nickel atom is located in a square-planar arrange-
ment of ligand functions. Bond lengths CϪNi and NϪNi
are as usual[5] but opposite N,P and C,P donor atoms devi-
ate from linearity by 10 and 20°, respectively. The chelate
bond NiϪP1 is by 8 pm longer than NiϪP2 due to the
(2)
The reaction mixture displays a deep red color, while re-
moval of THF solvent together with 1 mol-equiv. of trime-
thylphosphane during workup causes a change to orange-
yellow, finally yielding orange solids 3Ϫ5. The microcrystal-
line compounds are highly hygroscopic and under argon de-
compose above 122 °C, 105 °C, and 83 °C, respectively.
Using 2-(diisopropylphosphanyl)-N-methylaniline in a
similar synthesis [Equation (3)] affords red crystals of 6 that
decompose above 104 °C. NMR spectra of THF solutions
of 3Ϫ6 again each display a double set of the expected res-
onances which are assigned to cis and trans isomers. In par-
ticular, NiCH3 protons opposite to the chelating 31P donor
resonate between δ ϭ Ϫ0.82 and Ϫ0.77 ppm with unre-
3
solved trans coupling (cis JP,H ϭ 4.5Ϫ6.1 Hz) while for
those opposite to the amide donor at δ ϭ Ϫ0.04(3) ppm a
doublet of doublets pattern is observed (3JP,H
ϭ
3.8Ϫ4.1 Hz). In toluene solution the trans isomers are ob-
served as the dominant species (Ͼ 95%).
Figure 1. 31P NMR spectra of 3 (THF, 213Ϫ298K)
Eur. J. Inorg. Chem. 2003, 232Ϫ239
233

H.-F. Klein, R. Beck, O. Hetche
FULL PAPER
larger trans influence of the NiMe group relative to the 5 (530.0°) suggesting a better fit of the former and a slight
amide donor. The Me3Si group is clearly oriented above the thermodynamic advantage for the pentacoordinate com-
plane of the metallacycle.
plex molecule.
Figure 3. Molecular structure of 7 (ORTEP plot with hydrogen
˚
atoms omitted); selected bond lengths [A] and angles [°]: NiϪC20
Figure 2. Molecular structure of cis-5 (ORTEP plot with hydrogen
1.996(6), NiϪN 1.974(4), NiϪP1 2.202(2), NiϪP2 2.224(2), NiϪP3
2.253(2), NϪC1 1.452(6), NϪC19 1.452(6), C1ϪC2 1.423(7);
NϪNiϪC20 176.7(3), P1ϪNiϪP2 125.90(6), P1ϪNiϪP3
˚
atoms omitted); selected bond lengths [A] and angles [°]: NiϪC1
1.971(11), NiϪN 1.956(8), NiϪP1 2.219(3), NiϪP2 2.124(3),
P1ϪC9 1.814(10), C9ϪC14 1.387(15), C14ϪN 1.367(14), NϪSi
1.731(8); NϪNiϪP2 170.0(3), NϪNiϪP1 84.0(3), C1ϪNiϪP1
160.8(4), NϪNiϪC1 91.6(4), P1ϪNiϪP2 102.26(11), C1ϪNiϪP2
84.9(4), C9ϪP1ϪNi 96.3(3), C14ϪNϪNi 117.6(6), SiϪNϪNi
115.8(5), C14ϪNϪSi 123.6(6)
110.71(6),
P2ϪNiϪP3
123.36(7),
P1ϪNiϪN
85.60(13),
P1ϪNiϪC20 91.1(2), NiϪNϪC1 120.9(3), C1ϪNϪC19 116.5(4),
NiϪNϪC19 122.3(3)
A prochiral P-donor function was introduced using 2-
[tert-butyl(phenyl)phosphanyl]-N-methylaniline as a preche-
late reactant [Equation (4)]. The red crystals of pentacoord-
inate 9 are highly soluble in pentane and under argon de-
compose above 115 °C.
Added trimethylphosphane makes 3 and 4 better soluble
in pentane and causes a deep red color. Upon cooling, dark
red crystals of 7 and 8 are isolated that show an even better
thermal stability than their parent complexes reminding one
of the pair NiMe2(PMe3)2 and NiMe2(PMe3)3.[6] Only 6
does not change color under these conditions and is reco-
vered unchanged. Analytical and spectroscopic data are
consistent with pentacoordinate compounds 7 and 8. In so-
lution dissociation of the ligands is excessive, and in 31P
NMR experiments a low-temperature limit of ligand mo-
tions was only attained with 7 revealing the coordination
geometry. A doublet at δ ϭ Ϫ16 ppm (2 P) for trimethyl-
phosphane and a triplet at δ ϭ 23 ppm for the PPh2 group
(4)
2
with JP,P ϭ 192 Hz are consistent with all three phos-
phorus donor atoms in equatorial sites leaving methyl and
amide groups in axial positions of a trigonal bipyramid.
One bulky alkyl substituent in the 2-(phosphanyl) group
does not interfere with the reversible uptake of trimethyl-
The molecular structure (Figure 3) confirms the config- phosphane. With 9 we have not been able to isolate a 16-
uration of 7 as derived from spectroscopic data. The nickel VE species in an analytically pure state.
atom is centered in a trigonal bipyramid with axial C and
A close structural relationship between 8 and [2-(di-
N and three equatorial P donor atoms. Bond lengths are phenylphosphanyl)phenolato-O,P]methylbis(trimethylphos-
not notably different from those in cis-5, and the chelate phane)nickel[7] is found in agreement with expectation for
bite angle [P1ϪNiϪN 85.60(13)°] is only slightly larger isoelectronic molecules (Table 1).
than in cis-5 [P1ϪNiϪN 84.0(3)°]. A difference is recog-
Ligand mobility in P,N-chelates of nickel appears to be
nized in a trigonal-planar arrangement of bonds to N in 7 generally higher than in P,O-chelates, but only the first dis-
(sum of angles 359.7°) as compared with a more pyramidal sociation step (Scheme 2) could be demonstrated by experi-
geometry in cis-5 (sum of angles 357.0°). Interestingly, the ment.
sum of internal angles in the metallacycle of 7 (539.7°) is
While removal of the second trimethylphosphane ligand
closer to the value of a regular pentagon (540°) than in cis- was achieved with P,O-chelating ligands by formation of µ2-
234
Eur. J. Inorg. Chem. 2003, 232Ϫ239

Dynamic Properties of Methyl(trimethylphosphane)nickel Complexes
FULL PAPER
Table 1. Structural relations between isoelectronic P,O and P,N compounds of nickel()
X ϭ O[7]
X ϭ NMe (8)
Selected bond lenghts [pm]:
NiϪC(1)
NiϪP(1)
NiϪP(2)
NiϪP(3)
NiϪX
198.1(5)
219.1(2)
224.5(2)
222.4(2)
198.4(3)
199.6(6)
220.2(2)
225.3(2)
222.4(2)
197.4(4)
Selected bond angles [°]:
XϪNiϪC(1)
XϪNiϪP(1)
P(1)ϪNiϪP(3)
P(1)ϪNiϪP(2)
P(3)ϪNiϪP(2)
Σ five-membered metallacycle [°]:
177.7(2)
86.35(10)
125.16(6)
114.02(6)
120.71(7)
538.8
176.7(3)
85.60(13)
125.90(6)
110.71(6)
123.36(7)
539.7
Conclusion
Methyl(trimethylphosphane)nickel complexes of P,N-
chelating 2-(phosphanyl)anilines can be smoothly synthe-
sized from convenient starting compounds as thermally
stable materials. Solution dynamics of ligand motions and
solvent-dependent equilibria of square-planar cis and trans
isomers are novel and characteristic properties when com-
pared with isoelectronic P,O-chelates. Rapid addition and
dissociation of trimethylphosphane exclusively involve
equatorial positions of a trigonal bipyramid with axial
methyl and N-donor groups. Replacing an oxygen by a ni-
trogen donor atom in five-membered metallacycles of nickel
brings about gross electronic changes whereby catalytic ac-
tivity in oligomerization of ethene is completely lost. A
coarse tuning by electronic effects of substituents attached
to the metallacycle would be necessary to recover such ac-
tivity.
Scheme 2. Dynamic coordination in methylnickel P,N-chelates
O-bridged dinuclear complexes,[8] our attempts to remove
the last trimethylphosphane ligand from the metal atom by
favoring a bridging coordination mode of the amide func-
tion met with thermal decomposition (in boiling toluene). Experimental Section
However, this result does not exclude a 14-electron species
as an intermediate providing still another vacant coordina-
tion site for substrate binding.
General Procedures and Materials: All air-sensitive and volatile
materials were handled using standard vacuum techniques and
were kept under argon. Microanalyses: Kolbe Microanalytical
Laboratory, Mülheim/Ruhr, FRG. Melting points/decomposition
temperatures: Sealed capillaries, uncorrected values. Chemicals
(Merck/Schuchardt) were used as purchased. Literature methods
were applied in the preparation of NiCl2(PMe3)2, Ni-
MeCl(PMe3)2,[6] 2-(diphenylphosphanyl)aniline,[9] 2-(diphenylpho-
sphanyl)-N-methylaniline, 2-(diisopopylphosphanyl)aniline[10] and
2-[tert-butyl(phenyl)phosphanyl]-N-methylaniline.[11] IR: Nujol
mulls between KBr discs, Bruker spectrophotometer type FRA
Therefore, the tetracoordinate complexes 3Ϫ5 as prime
candidates were examined with respect to catalytic activity
in ethene oligomerization under otherwise same conditions
as with the isoelectronic and highly active P,O-chelates.[7]
A
toluene solution (80 mL) containing 0.1 mmol of complex
was kept in a steel autoclave under 50 bar of ethene at 80
°C. No drop of pressure was observed within 12 h which
corresponds with no activity.
Eur. J. Inorg. Chem. 2003, 232Ϫ239
235

H.-F. Klein, R. Beck, O. Hetche
FULL PAPER
106. 1H and 13C NMR spectra (300 MHz and 75 MHz, respect-
2.40 mmol) in 50 mL of THF causing the red color to turn green.
ively) were recorded with a Bruker ARX-300 spectrometer, 31P The mixture was warmed to 20 °C, stirred for 3 h, and concentrated
NMR spectra (81 MHz) with a Bruker AM-200 instrument. 13C
and 31P resonances were obtained with broad-band proton decoup-
ling.
to dryness in vacuo. The residue was extracted with three 80-mL
portions of diethyl ether and the green solution cooled to 4 °C to
afford green rectangular crystals. Yield 745 mg (60%); m.p.
108Ϫ109 °C (dec.). 1H NMR (200 MHz, [D8]THF, 233 K): cis-2
2-(Diphenylphosphanyl)-N-(trimethylsilyl)aniline: 2-(Diphenylphos-
phanyl)aniline (1.20 g, 4.32 mmol) in diethyl ether (80 mL) was
combined with 1.6  BuLi solution in hexane (2.7 mL, 4.32 mmol)
and kept at 20 °C for 30 min. Chlorotrimethylsilane (470 mg,
4.32 mmol) was added, and after 16 h, LiCl was filtered off and the
solution concentrated to a volume of 40 mL. Cooling to 4 °C af-
2
(66%): δ ϭ 0.02 (s, 9 H, SiCH3), 1.06 (d, JP,H ϭ 9.2 Hz, 9 H,
PCH3), 5.93 (m, 1 H, CH), 6.23 (m, 1 H, CH), 6.71 (m, 2 H, CH),
6.83 (m, 2 H, CH), 7.41Ϫ7.49 (m, 6 H, CH), 7.76Ϫ7.85 (m, 4 H,
2
CH); trans-2 (34%): δ ϭ 0.06 (s, 9 H, SiCH3), 1.39 (d, JP,H
ϭ
11.1 Hz, 9 H, PCH3), 6.15 (m, 1 H, CH), 6.40 (m 1 H, CH), 7.05
(m, 2 H, CH), 7.49Ϫ7.58 (m, 6 H, CH), 8.00Ϫ8.02 (m, 4 H, CH)
ppm. 31P NMR (81 MHz, [D8]THF, 233 K): cis-2 (66%): δ ϭ Ϫ8
forded white crystals. Yield 1.10 g (73%); m.p. 76Ϫ77 °C. 1H NMR
4
(300 MHz, [D8]THF): δ ϭ 0.01 (s, 9 H, SiCH3), 4.30 (d, JP,H
ϭ
2
2
(d, JP,P ϭ 88 Hz, 1 P, PCH3), 52 (d, JP,P ϭ 88 Hz, 1 P, PC6H5);
trans-2 (34%): δ ϭ Ϫ9 (d, 2JP,P ϭ 348 Hz, 1 P, PCH3), 32 (d, 2JP,P ϭ
348 Hz, 1 P, PC6H5) ppm. C24H32ClNNiP2Si (517.1): calcd. C
55.57, H 6.22, N 2.70, P 11.94; found C 55.18, H 5.78, N 2.66,
P 11.95.
3
4
9.3 Hz, 1 H, NH), 6.45 (dt, J ϭ 7.6, J ϭ 0.7 Hz, 1 H, CH), 6.65
(m, 2 H, CH), 7.01 (dt, 3J ϭ 6.5, 4J ϭ 1.5 Hz, 2 H, CH), 7.13Ϫ7.20
(m, 10 H, CH) ppm. 13C NMR (75 MHz, [D8]THF): δ ϭ Ϫ1.89
4
(s, CH3), 114.7 (s, CH), 116.9 (d, JP,C ϭ 2.2 Hz, CH), 120.9 (d,
3JP,C ϭ 5.6 Hz, C), 127.4 (s, CH), 127.6 (d, JP,C ϭ 7.8 Hz, CH),
2
1
3
129.1 (s, CH), 132.5 (d, JP,C ϭ18.7 Hz, CH), 133.7 (d, JP,C
ϭ
[2-(Diphenylphosphanyl)anilido-N,P](methyl)(trimethylphosphane)-
nickel (3): 2-(Diphenylphosphanyl)aniline (910 mg, 3.28 mmol) in
70 mL of diethyl ether was combined at Ϫ70 °C with 1.6  MeLi
in diethyl ether (2.1 mL, 3.28 mmol), and this solution was added
dropwise at Ϫ70 °C to NiMeCl(PMe3)2 (860 mg, 3.28 mmol) in
50 mL of diethyl ether. The mixture was warmed to 20 °C and
concentrated to dryness in vacuo. The resulting orange solid was
extracted with three 70-mL portions of fresh diethyl ether and the
solution concentrated at 20 °C to afford orange crystals of 3
(358 mg). From the mother liquor at Ϫ27 °C a light yellow solid
(632 mg) was obtained which consisted of 3 only (NMR). Com-
bined yields 990 mg (71%); m.p. 105Ϫ106 °C (dec.). IR (Nujol):
ν˜ ϭ 3348 cmϪ1 (NϪH). 1H NMR (300 MHz, [D8]THF): cis-3
2
1
5.5 Hz, C), 135.1 (d, JP,C ϭ 7.7 Hz, C), 150.1 (d, JP,C ϭ 19.5 Hz,
CH) ppm. 31P NMR (81 MHz, [D8]THF): δ ϭ Ϫ10 (s) ppm.
C21H24NPSi (349.5): calcd. C 72.17, H 6.92, N 4.01; found C 72.45,
H 6.63, N 3.95.
2-[tert-Butyl(phenyl)phosphanyl]-N-methylaniline: This prechelate li-
gand was obtained in a procedure given for 2-(diphenylphos-
phanyl)-N-methylaniline[10] starting from N-methylaniline and
chloro(tert-butyl)phenylphosphane. Yield 52%, yellow oil; b.p.
189Ϫ190 °C/7 mbar. IR (Nujol, 4000Ϫ400 cmϪ1): ν˜ ϭ 3349 vs
(νNϪH), 3052 m, 2926 m (νHϪCϭ), 2810 (νNCϪH), 1587 s, 1569
s (νCϭC), 1518 s, 1454 s, 1435 s, 1419 m, 1312 m (δasPCH), 1289
m (δsPCH), 1165 m, 1089 w, 1046 w, 1029 vw, 999 vw, 912 vw, 746
vs, 729 w, 698 vs (γCϪH), 515 m, 496 m, 482 m. 31P NMR
(81 MHz, CD2Cl2, 296 K): δ ϭ Ϫ16 (s) ppm.
(60%): δ ϭ Ϫ0.07 (dd,
NiCH3), 1.29 (d, JP,H ϭ 3.6 Hz, 9 H, PCH3), 3.44 (s, 1 H, NH),
5.85 (m, 1 H, CH), 6.64Ϫ6.67 (m, 1 H, CH), 6.85 (t, J ϭ 6.9 Hz,
3JP,H ϭ 4.1, 3JP,H ϭ 8.8 Hz, 3 H,
trans
cis
2
3
1 H, CH), 7.31 (m, 1 H, CH), 7.33Ϫ7.36 (m, 6 H, CH), 7.62Ϫ7.67
Chloro[2-(diphenylphosphanyl)anilido-N,P](trimethylphosphane)-
nickel (1): 2-(Diphenylphosphanyl)aniline (750 mg, 2.70 mmol) in
50 mL of THF was combined at Ϫ70 °C with 1.6  MeLi in diethyl
ether (1.7 mL, 2.70 mmol), and this solution was added dropwise
at Ϫ70 °C to NiCl2(PMe3)2 (762 mg, 2.70 mmol) in 50 mL of THF
causing the red color to turn green. The mixture was warmed to
20 °C and concentrated to dryness in vacuo. The solid residue was
extracted with three 80-mL portions of diethyl ether through a
glass-sinter disc (G3) and the green solution cooled to 4 °C to af-
ford green crystals. Yield 710 mg (59%); m.p. 95Ϫ96 °C (dec.). IR
(Nujol): ν˜ ϭ 3377 cmϪ1 (NϪH). 1H NMR (200 MHz, [D8]THF,
3
(m, 4 H, CH); trans-3 (40%): δ ϭ Ϫ0.82 (d, JP,H ϭ 6.1 Hz, 3 H,
2
NiCH3), 1.09 (d, JP,H ϭ 8.6 Hz, 9 H, PCH3), 3.06 (s, 1 H, NH),
5.88 (dd, 3Jϭ 7.0, 4Jϭ 1.4 Hz, 1 H, CH), 5.91 (dd, 3J ϭ 8.2, 4JP,H ϭ
5.0 Hz, 1 H, CH), 6.64Ϫ6.67 (m, 2 H, CH), 7.36Ϫ7.41 (m, 6 H,
CH), 7.70Ϫ7.77 (m, 4 H, CH) ppm. 13C NMR (75.4 MHz,
2
2
[D8]THF, 296 K): cis-3 (60%): δ ϭ 4.2 (dd, JP,C ϭ 33.8, JP,C
ϭ
62.6 Hz, NiCH3), 12.6 (d, 1JP,C ϭ 21.9 Hz, PCH3), 108.8 (d, 3JP,C ϭ
6.2 Hz, C-2), 115.9 (d, JP,C ϭ 9.5 Hz, m-C), 128.9 (d, JP,C
2
2
ϭ
2
9.3 Hz, p-C), 130.2 (s, C-5), 134.1 (d, JP,C ϭ 11.4 Hz, o-C), 134.3
(s, C-3), 134.7 (s, i-C), 134.9 s, C-6), 171.4 (d, 2JP,C ϭ 31.0 Hz, NC-
2
2
1); trans-3 (40%): δ ϭ Ϫ16.8 (d, JP,C ϭ 24.1 Hz, NiCH3), 16.3 (d,
233 K): cis-1 (63%): δ ϭ 1.07 (d, JP,H ϭ 10.1, 9 H, PCH3), 3.65
1JP,C ϭ 28.9 Hz, PCH3), 110.4 (d, JP,C ϭ 5.6 Hz, C-2), 114.8 (d,
3
(s, 1 H, NH), 5.91 (m, 1 H, CH), 6.22 (m, 1 H, CH), 6.67 (m, 1 H,
CH), 7.15 (m, 1 H, CH), 7.45Ϫ7.55 (m, 6 H, CH), 7.82Ϫ7.86 (m,
4 H, CH); trans-1 (37%): δ ϭ 1.33 (d, 2JP,H ϭ 10.0 Hz, 9 H, PCH3),
4.59 (s, 1 H, NH), 6.10 (m, 1 H, CH), 6.37 (m, 1 H, CH), 6.67 (m,
1 H, CH), 7.01 (m, 1 H, CH), 7.15 (m, 1 H, CH), 7.31 (m, 1 H,
CH), 7.55Ϫ7.59 (m, 6 H, CH), 7.98Ϫ8.07 (m, 4 H, CH) ppm. 31P
3JP,C ϭ 3.0 Hz, C-5), 128.9 (d, 2JP,C ϭ 8.6 Hz, m-C), 130.4 (s, p-C),
2
132.6 (d, JP,C ϭ 10.2 Hz, o-C), 133.2 (s, C-3), 134.7 (s, C-4), 134.9
(s, i-C), 135.2 (s, C-6), 169.9 (d, JP,C ϭ 32.7 Hz, NC-1) ppm. 31P
2
2
NMR (81 MHz, [D8]THF): cis-1 (60%, 193 K): δ ϭ Ϫ2 (d, JP,P
ϭ
27 Hz, 1 P, PCH3), 40 (d, 2JP,P ϭ 27 Hz, 1 P, PC6H5); trans-3 (40%,
2
2
NMR (81 MHz, [D8]THF, 233 K): cis-1 (63%): δ ϭ Ϫ9 (d, 2JP,P
ϭ
193 K): δ ϭ Ϫ2 (d, JP,P ϭ 303 Hz, 1 P, PCH3), 40 (d, JP,P
ϭ
303 Hz, 1 P, PC6H5); cis-1 (60%, 296 K): δ ϭ Ϫ2 (d, 2JP,P ϭ 25 Hz,
1 P, PCH3), 40 (d, 2JP,P ϭ 25 Hz, 1 P, PC6H5); trans-3 (40%, 296 K):
δ ϭ Ϫ5 (s, 1 P, PCH3), 37 (s, 1 P, PC6H5) ppm. C22H27NNiP2
(425.1): calcd. C 62.01, H 6.38, N 3.28, P 14.53; found C 61.52, H
6.51, N 3.16, P 14.48.
89 Hz, 1 P, PCH3), 52 (d, 2JP,P ϭ 89 Hz, 1 P, PC6H5); trans-1 (37%):
2
δ ϭ Ϫ9 (d, 2JP,P ϭ 347 Hz, 1 P, PCH3), 31 (d, JP,P ϭ 347 Hz, 1 P,
PC6H5) ppm. C21H24ClNNiP2 (445.0): calcd. C 56.49, H 5.42, N
3.14; found C 56.68, H 5.50, N 3.05.
Chloro[2-(diphenylphosphanyl)-N-(trimethylsilyl)anilido-N,P](tri-
methylphosphane)nickel (2): 2-(Diphenylphosphanyl)-N-(trimethyl-
[2-(Diphenylphosphanyl)-N-methylanilido-N,P](methyl)(trimethyl-
silyl)aniline (840 mg, 2.40 mmol) in 50 mL of THF was combined phosphane)nickel (4): 2-(Diphenylphosphanyl)-N-methylaniline
at Ϫ70 °C with 1.6  MeLi in diethyl ether (1.5 mL, 2.40 mmol),
and this solution was added as above to NiCl2(PMe3)2 (677 mg,
(970 mg, 3.32 mmol) in 50 mL of diethyl ether was combined at
Ϫ70 °C with 1.6  MeLi in diethyl ether (2.2 mL, 3.32 mmol), and
236
Eur. J. Inorg. Chem. 2003, 232Ϫ239

Dynamic Properties of Methyl(trimethylphosphane)nickel Complexes
this solution was added dropwise at Ϫ70 °C to NiMeCl(PMe3)2 centrated to dryness in vacuo. The resulting orange solid was ex-
FULL PAPER
(870 mg, 3.32 mmol) in 80 mL of diethyl ether. The orange-red
mixture was warmed to 20 °C, filtered, and concentrated to dryness
in vacuo. The resulting solid was washed with 5 mL of pentane and
dried at 20 °C in vacuo to afford a yellow solid of 4 (1.18 g). Single
tracted with two 50-mL portions of pentane, and the combined
solutions after repeatedly concentrating and cooling to Ϫ27 °C af-
forded red crystals of 6 (751 mg). Yield 58%; m.p. 104Ϫ105 °C
1
(dec.). H NMR (300 MHz, [D8]THF, 296 K): trans-6 (78%): δ ϭ
2
orange crystals obtained from toluene were found suitable for X- Ϫ0.65 (d, 3JP,H ϭ 9.1 Hz, 3 H, NiCH3), 1.00 (d, JP,H ϭ 3.6 Hz, 18
ray diffraction. Yield 71%; m.p. 122Ϫ124 °C (dec.). 1H NMR H, PCH3), 2.67 (s, 3 H, NCH3), 5.82 (m, 1 H, CH), 5.89 (d, J ϭ
3
(300 MHz, [D8]THF): cis-4 (88%): δ ϭ 0.13 (m, 3 H, NiCH3), 1.15 7.2 Hz, 1 H, CH), 6.57Ϫ6.63 (m, 2 H, CH), 7.22Ϫ7.27 (m, 6 H,
2
(d, JP,H ϭ 6.9 Hz, 9 H, PCH3), 2.60 (s, 3 H, NCH3), 5.89 (m, 1 CH), 7.46Ϫ 7.48 (m, 4 H, CH); cis-6 (22%): δ ϭ Ϫ0.07 (dd,
H, CH), 6.15 (m, 1 H, CH), 6.62 (m, 1 H, CH), 6.84 (m, 1 H, CH),
3JP,H ϭ 3.7, 3JP,H ϭ 6.5 Hz, 3 H, NiCH3), 1.00 (br. s, 9 H,
cis
trans
7.39 (m, 6 H, CH), 7.59Ϫ7.73 (m, 4 H, CH); trans-4 (12%): δ ϭ PCH3), 2.48 (s, 3 H, NCH3). 1H NMR (300 MHz, [D8]toluene):
2
3
Ϫ0.77 (m, 3 H, NiCH3), 1.05 (d, JP,H ϭ 8.9 Hz, 9 H, PCH3), 2.80
trans-6 (Ͼ 98%): δ ϭ 0.33 (dd, JP,H ϭ 4.1 and 8.2 Hz, 3 H,
(s, NCH3) ppm. 13C NMR (75.4 MHz, [D8]THF, 296 K): cis-4: δ ϭ NiCH3), 1.00 (d, JP,H ϭ 6.2 Hz, 9 H, PCH3), 1.24 (br. d, JP,H
ϭ
2
3
1
4.9 (m, NiCH3), 14.5 (d, JP,C ϭ 30.6 Hz, PCH3), 35.2 (s, NCH3), 7.1 Hz, 6 H, PCHCH3), 1.28 (br. d, 3JP,H ϭ 7.1 Hz, 6 H, PCHCH3),
1
3
108.4 (s, C-2), 108.7 (s, C-5), 127.1 (d, JP,C ϭ 16.9 Hz, m-C), 2.34 (m, 2 H, PCH), 2.98 (s, 3 H, NCH3), 6.40 (t, J ϭ 7.1 Hz, 1
1
3
4
3
127.4Ϫ131.1 (m, C-3/C-4), 131.7 (d, JP,C ϭ 26.7 Hz, o-C), 132.2
H, CH), 6.49 (dd, J ϭ 8.4, J ϭ 2.2 Hz, 1 H, CH), 7.12 (t, J ϭ
2
4
(d, JP,C ϭ 12.1 Hz, p-C), 153.6 (s, C-6) ppm. 31P NMR (81 MHz, 7.4 Hz, 1 H, CH), 7.31 (dt, 3J ϭ 7.1, JP,H ϭ 1.4 Hz, 1 H, CH)
2
[D8]THF, 233 K): cis-4 (88%): δ ϭ Ϫ1 (d, JP,P ϭ 32 Hz, 1 P,
ppm. 13C NMR (75.4 MHz, [D8]THF, 296 K): trans-6: δ ϭ Ϫ14.3
2
2
1
PCH3), 38 (d, JP,P ϭ 32 Hz, 1 P, PC6H5); trans-4 (12%): δ ϭ Ϫ9 (d, JP,C ϭ 16.8 Hz, NiCH3), 16.7 (d, JP,C ϭ 7.6 Hz, PCH3), 44.4
2
2
(d, JP,P ϭ 329 Hz, 1 P, PCH3), 34 (d, JP,P ϭ 329 Hz, 1 P, PC6H5)
(s, NCH3), 108.5 (s, C-2), 110.4 (d, 2JP,C ϭ 12.5 Hz, 5-C), 128.9 (d,
ppm. C22H27NNiP2 (425.1): calcd. C 62.76, H 6.64, N 3.18, P 2JP,C ϭ 8.6 Hz, m-C), 129.4Ϫ131.9 (m, p-C/C-3), 133.3 (d, JP,C
ϭ
2
2
14.07; found C 63.15, H 7.19, N 3.04, P 13.70.
11.5 Hz, o-C), 134.4 (d, JP,C ϭ 12.4 Hz, C-4), 135.3 (s, i-C), 139.8
(s, C-6) ppm. 31P NMR (81 MHz, [D8]THF, 193 K): trans-6 (78%):
2
2
[2-(Diphenylphosphanyl)-N-(trimethylsilyl)anilido-N,P](methyl)-
(trimethylphosphane)nickel (5): 2-(Diphenylphosphanyl)-N-(trime-
thylsilyl)aniline (830 mg, 2.37 mmol) in 80 mL of diethyl ether was
combined at Ϫ70 °C with 1.6  MeLi in diethyl ether (1.5 mL,
2.40 mmol), and to the fluorescent solution was added at Ϫ70 °C
solid NiMeCl(PMe3)2 (620 mg, 2.37 mmol) to form a deep red mix-
ture. The mixture was warmed to 20 °C, stirred for 1 h, and concen-
trated to dryness in vacuo. The residue was extracted with two 70-
mL portions of diethyl ether and the red solution cooled to Ϫ27
δ ϭ Ϫ11 (d, JP,P ϭ 326 Hz, 1 P, PCH3), 45 (d, JP,P ϭ 297 Hz, 1
2
P, PCHCH3); cis-1 (22%): δ ϭ Ϫ1 (d, JP,P ϭ 25 Hz, 1 P, PCH3),
45 (d, JP,P ϭ 25 Hz, 1 P, PCHCH3) ppm. 31P NMR (81 MHz,
2
2
[D8]toluene): trans-6 (Ͼ 98%): δ ϭ Ϫ18 (d, JP,P ϭ 327 Hz, 1 P,
PCH3), 40 (d, JP,P ϭ 327 Hz, 1 P, PCHCH3) ppm. C17H33NNiP2
2
(371.1): calcd. C 54.87, H 8.94, N 3.76, P 16.65; found C 54.88, H
8.83, N 3.71, P 16.70.
[2-(Diphenylphosphanyl)anilido-N,P](methyl)bis(trimethylphos-
°C to afford deep orange crystals of 5 (732 mg). Yield 62%; m.p. phane)nickel
(7):
2-(Diphenylphosphanyl)aniline
(810 mg,
1
83Ϫ84 °C (dec.). H NMR (300 MHz, [D8]THF): cis-5 (58%): δ ϭ
2.92 mmol) in 50 mL of diethyl ether was combined at Ϫ70 °C with
Ϫ0.01 (dd, trans3JP,H ϭ 3.8 Hz, cis3JP,H ϭ 8.8 Hz, 3 H, NiCH3), 0.09 1.6  MeLi in diethyl ether (1.8 mL, 2.92 mmol), and this solution
2
(s, 9 H, SiCH3), 1.09 (d, JP,H ϭ 4.1 Hz, 9 H, PCH3), 5.86 (m, 1 was added dropwise at Ϫ70 °C to NiMeCl(PMe3)2 (763 mg,
H, CH), 6.55 (m, 1 H, CH), 6.75 (m, 1 H, CH), 7.25 (m, 1 H, CH), 2.92 mmol) in 50 mL of diethyl ether. Workup proceeded as with 3,
7.31Ϫ7.35 (m, 6 H, CH), 7.64Ϫ7.70 (m, 4 H, CH); trans-5 (42%): and crystallization from 70 mL of pentane, containing excess PMe3
3
δ ϭ 0.82 (d, JP,H ϭ 4.5 Hz, 3 H, NiCH3), 0.07 (s, 9 H, SiCH3),
(1.23 g, 16.1 mmol), afforded dark red crystals that were dried in
2
1.08 (d, JP,H ϭ 8.6 Hz, 9 H, PCH3), 5.88 (m, 1 H, CH), 6.19 (dd, vacuo at Ϫ5 °C for 10 min. Yield 790 mg of 7 (54%); m.p. 110Ϫ111
3J ϭ 8.0, 4J ϭ 4.7 Hz, 1 H, CH), 6.55Ϫ6.63 (m, 1 H, CH), 6.85 °C (dec.). IR (Nujol): ν˜ ϭ 3361 cmϪ1 (NϪH). 1H NMR (300 MHz,
3
(m, 1 H, CH), 7.36Ϫ7.41 (m, 6 H, CH), 7.71Ϫ7.77 (m, 4 H, CH) [D8]THF, 296 K): trans-7 (66%): δ ϭ Ϫ0.75 (d, JP,H ϭ 8.6 Hz, 3
ppm. 13C NMR (75.4 MHz, [D8]THF): cis-5 (58%): δ ϭ 1.6 (s,
H, NiCH3), 1.00 (d, 2JP,H ϭ 3.6 Hz, 18 H, PCH3), 2.78 (NH 3,44s,
SiCH3), 4.2 (m, NiCH3), 12.7 (d, 1JP,C ϭ 21.9 Hz, PCH3), 110.8 (s, 1 H, NH), 5.86 (m, 1 H, CH), 6.19 (dd, J ϭ 6.2, J ϭ 1.6 Hz, 1
3
4
2
C-2), 115.9 (s, C-5), 129.3 (d, JP,C ϭ 9.2 Hz, m-C), 133.2Ϫ134.6 H, CH), 6.66 (m, 1 H, CH), 6.85 (m, 1 H, CH), 7.30Ϫ7.38 (m, 6
(s, C-1, o-C, p-C), 135.0 (s, C-6), 172.3 (d, JP,C ϭ 31.5 Hz, NC-1); H, CH), 7.64Ϫ7.74 (m, 4 H, CH); cis-7 (34%): δ ϭ Ϫ0.06 (m, 3 H,
trans-5 (42%): δ ϭ Ϫ16.9 (d, JP,C ϭ 24.9 Hz, NiCH3), 1.9 (s,
SiCH3), 16.1 (d, JP,C ϭ 25.9 Hz, PCH3), 111.2 (d, JP,C ϭ 6.1 Hz,
C-2), 114.8 (s, C-5), 129.0 (s, C-3), 130.5 (d, JP,C ϭ 18.7 Hz, o-C), [D8]THF, 296 K): trans-7: δ ϭ Ϫ14.1 (m, NiCH3), 16.7 (d, JP,C
132.7 (d, JP,C ϭ 9.8 Hz, m-C), 133.2 (s, p-C), 134.1 (d, JP,C
2
2
2
NiCH3), 1.00 (d, JP,H ϭ 3.6 Hz, 9 H, PCH3), 3.44 (s, 1 H, NH),
1
3
5.88 (m, 1 H, CH), 6.20 (m, 1 H, CH) ppm. 13C NMR (75.4 MHz,
2
1
ϭ
2
2
ϭ
7.2 Hz, PCH3), 45.1 (s, NCH3), 108.5Ϫ135.4 (s, 10 C) ppm. 31P
NMR (81 MHz, [D8]THF, 233 K): trans-7 (66%): δ ϭ Ϫ26 (br. s,
2
11.9 Hz, i-C), 134.7 (s, C-4), 135.2 (s, C-6), 171.2 (d, JP,C
ϭ
30.8 Hz, NC-1) ppm. 31P NMR (81 MHz, [D8]THF, 233 K) cis-5
2 P, PCH3), 27 (br. s, 1 P, PC6H5); cis-7 (34%): δ ϭ Ϫ1 (d, JP,P ϭ
2
2
2
2
(58%): δ ϭ 1 (d, JP,P ϭ 27 Hz, 1 P, PCH3), 40 (d, JP,P ϭ 27 Hz, 26 Hz, 1 P, PCH3), 39 (d, JP,P ϭ 26 Hz, 1 P, PC6H5) ppm.
1 P, PC6H5); trans-5 (42%): δ ϭ Ϫ3 (d, 2JP,P ϭ 297 Hz, 1 P, PCH3),
C25H35NNiP3 (501.1): calcd. C 59.79, H 7.23, N 2.79, P 18.50;
2
40 (d, JP,P ϭ 297 Hz, 1 P, PC6H5) ppm. C25H35NNiP2Si (497.1): found C 58.80, H 7.39, N 2.74, P 18.33.
calcd. C 6.26, H 7.08, N 2.81, P 12.40; found C 60.36, H 6.75, N
2.78, P 12.15.
[2-(Diphenylphosphanyl)-N-methylanilido-N,P](methyl)bis-
(trimethylphosphane)nickel (8). Method a: 2-(Diphenylphosphanyl)-
N-methylaniline (845 mg, 2.90 mmol) in 70 mL of THF was com-
bined at Ϫ70 °C with NiMe2(PMe3)3 (920 mg, 2.90 mmol) in
80 mL of diethyl ether. Warming to 20 °C caused evolution of gas
and a dark red color. After 3 h, the volatiles were removed in vacuo
[2-(Diisopropylphosphanyl)-N-methylanilido-N,P](methyl)(trimeth-
ylphosphane)nickel (6): 2-(Diphenylphosphanyl)-N-methylaniline
(780 mg, 3.49 mmol) in 50 mL of diethyl ether was combined at
Ϫ70 °C with 1.6  MeLi in diethyl ether (2.3 mL, 3.50 mmol), and
to the yellow fluorescent solution was added solid NiMeCl(PMe3)2 and the residue was extracted with 70 mL of pentane, containing
(912 mg, 3.49 mmol). The mixture was warmed to 20 °C and con-
Eur. J. Inorg. Chem. 2003, 232Ϫ239
excess PMe3 (610 mg, 8.0 mmol). Cooling to Ϫ27 °C afforded dark
237

H.-F. Klein, R. Beck, O. Hetche
FULL PAPER
red crystals of 8: Yield 478 mg (32%). Method b: 2-(Diphenylphos-
phanyl)-N-methylaniline (770 mg, 2.64 mmol) in 70 mL of diethyl
2
2
Ϫ16 (d, JP,P ϭ 181 Hz, 2 P, PCH3), 31 (t, JP,P ϭ 181 Hz, 1 P,
2
PC6H5); cis-9 (21%): δ ϭ Ϫ1 (d, JP,P ϭ 29 Hz, 1 P, PCH3), 57 (d,
ether was combined at Ϫ70 °C with 1.6  MeLi in diethyl ether 2JP,P ϭ 29 Hz, 1 P, PC6H5) ppm. C24H42NNiP3 (495.2): calcd. C
(1.7 mL, 2.64 mmol), and to the yellow fluorescent solution was
58.09, H 8.53, N 2.82, P 18.73; found C 58.06, H 8.40, N 2.73,
added NiMeCl(PMe3)2 (690 mg, 2.64 mmol) in 50 mL of diethyl P 18.70.
ether. The deep red mixture was warmed to 20 °C and after 3 h
concentrated to dryness in vacuo. The resulting solid was worked
Crystal Structure Analyses: Crystal data are presented in Table 2.
Data collection: Complex cis-5: A crystal was sealed under argon
in a glass capillary and mounted on a Stoe Stadi-4 diffractometer.
Reflections were collected (ω-scans) using graphite-monochrom-
ated Mo-Kα radiation; absorption corrections based on ψ-scans
were applied. The structure was solved by direct and conventional
Fourier methods. All non-hydrogen atoms were treated aniso-
tropically, hydrogen atoms were treated with a riding model in
idealized positions. The final wR2 value is high due to poor crystal
quality, but there is no doubt about the space group. Complex 7:
Crystal mounting, data collection, structure solution, and refine-
ment as for cis-5. Crystallographic data (excluding structure fac-
tors) for the structures reported in this paper have been deposited
with the Cambridge Crystallographic Data Centre. Copies of the
data [CCDC-186327 (cis-5) and -186328 (7)] can be obtained free
of charge on application to CCDC, 12 Union Road, Cambridge
up as above affording crystals of 8. Yield 912 mg (67%); m.p.
1
117Ϫ119 °C (dec.). H NMR (300 MHz, [D8]THF, 296 K): trans-8
3
(79%): δ ϭ Ϫ0.74 (d, JP,H ϭ 10.1 Hz, 3 H, NiCH3), 1.02 (d,
2JP,H ϭ 4.8 Hz, 18 H, PCH3), 1.24 (d, 2JP,H ϭ 12.6 Hz, 9 H, PCH3),
2.66 (s, 3 H, NCH3), 5.95 (t, 3J ϭ 7.2 Hz, 1 H, CH), 6.12 (dd,
4JP,H ϭ 5.0, 3J ϭ 8.5 Hz, 1 H, CH), 6.86 (dt, 3J ϭ 8.1, 4J ϭ 1.5 Hz,
1 H, CH), 7.22 (dt, 3J ϭ 7.4, 4J ϭ 1.5 Hz, 1 H, CH), 7.21Ϫ7.29
(m, 3 H, CH), 7.59Ϫ7.67 (m, 2 H, CH); cis-8 (21%): δ ϭ Ϫ0.07
3
3
2
(dd, JP,H ϭ 4.2, JP,H ϭ 8.2 Hz, 3 H, NiCH3), 1.12 (d, JP,H
ϭ
2
4.8 Hz, 9 H, PCH3), 1.47 (d, JP,H ϭ 13.2 Hz, 9 H, PCH3), 2.59 (s,
3 H, NCH3), 5.83 (t, 3J ϭ 7.1 Hz, 1 H, CH), 6.17 (dd, 4JP,H ϭ 5.2,
3J ϭ 8.2 Hz, 1 H, CH), 6.41 (dt, J ϭ 8.8, J ϭ 1.5 Hz, 1 H, CH),
6.86 (dt, 3J ϭ 8.1, 4J ϭ 1.5 Hz, 1 H, CH), 7.31Ϫ7.33 (m, 3 H, CH),
7.70Ϫ7.80 (m, 2 H, CH) ppm. 13C NMR (75.4 MHz, [D8]THF,
3
4
2
296 K): trans-8: δ ϭ Ϫ14.4 (d, JP,C ϭ 14.5 Hz, NiCH3), 16.3 (d,
CB2 1EZ, UK [Fax: (internat.)
deposit@ccdc.cam.ac.uk].
ϩ 44-1223/336-033, E-mail:
2JP,C ϭ 6.9 Hz, PCH3), 29.1 (d, JP,C ϭ 5.8 Hz, CCH3), 36.3 d
1
2JP,C ϭ 11.9 Hz, CCH3), 44.6 (s, NCH3), 107.5 (s, C-2), 110.1 (s,
2
C-5), 110.7 (d, JP,C ϭ 10.8 Hz, o-C), 127.9 (s, C-3), 128.5 (d,
3JP,C ϭ 6.8 Hz, p-C), 131.8 (s, C-4), 132.8 (d, 3JP,C ϭ 8.4 Hz, m-C),
133.9 (s, i-C), 134.8 (s, C-6), 170.5 (m, NC-1) ppm. 31P NMR
Table 2. Crystal data for compounds cis-5 and 7
2
(81 MHz, [D8]THF, 233 K): trans-8 (79%): δ ϭ Ϫ16 (d, JP,P
ϭ
181 Hz, 2 P, PCH3), 31 (t, 2JP,P ϭ 181 Hz, 1 P, PC6H5); cis-8 (21%):
cis-5
7
2
2
δ ϭ Ϫ1 (d, JP,P ϭ 29 Hz, 1 P, PCH3), 57 (d, JP,P ϭ 29 Hz, 1 P,
PC6H5) ppm. C26H38NNiP3 (515.2): calcd. C 60.49, H 7.42, N 2.71,
P 18.00; found C 60.71, H 7.30, N 2.75, P 18.10.
Empirical formula
Formula mass
Crystal size [mm]
Crystal system
Space group
C25H35NNiP2Si
498.4
0.38 ϫ 0.20 ϫ 0.19 0.41 ϫ 0.30 ϫ0.18
monoclinic
P21/c
10.6570(9)
18.9000(11)
26.19900(17)
90.870(5)
5276.32(40)
4
C26H38NNiP3
516.3
{2-[tert-Butyl(phenyl)phosphanyl]-N-methylanilido-N,P}(methyl)bis-
(trimethylphosphane)nickel (9): 2-[tert-Butyl(phenyl)phosphanyl]-N-
methylaniline (680 mg, 2.50 mmol) in 80 mL of diethyl ether was
treated at Ϫ 50 °C whilst stirring with 1.6  MeLi in diethyl ether
(1.6 mL, 2.50 mmol). After warming to 20 °C, the mixture was
stirred until evolution of gas had ceased. At Ϫ 50 °C this reagent
was combined with NiClMe(PMe3)2 (655 mg, 2.50 mmol) in 50 mL
of diethyl ether. The mixture was stirred at 20 °C for 3 h and con-
centrated to dryness in vacuo. The resulting orange solid was ex-
tracted with two 50-mL portions of pentane and the solution con-
centrated at 20 °C to afford short red rods of 9. Yield 583 mg
(47%), m.p. 115Ϫ117 °C (dec.). 1H NMR (300 MHz, [D8]THF,
296 K): trans-9 (79%): δ ϭ Ϫ0.74 (d, 3JP,H ϭ 10.1 Hz, 3 H, NiCH3),
monoclinic
P21/c
8.558(3)
19.911(10)
15.817(7)
93.13(3)
2726.2(2)
4
˚
a [A]
˚
b [A]
˚
c [A]
β [°]
3
˚
V [A ]
Z
Dcalcd. [g/cm3]
1.255
0.856
293(2)
1.255
0.843
293(2)
µ(Mo-Kα) [mmϪ1
T [K]
]
Data coll. range [°]
5.8 Յ 2Θ Յ 50
Ϫ10 Յ h Յ 10
0 Յ k Յ 18
0 Յ l Յ 25
4.9 Յ 2Θ Յ 50
Ϫ8 Յ h Յ 8
0 Յ k Յ 19
0 Յ l Յ 15
8166
h
k
l
2
2
1.02 (d, JP,H ϭ 4.8 Hz, 18 H, PCH3), 1.24 (d, JP,H ϭ 12.6 Hz, 9
H, PCH3), 2.66 (s, 3 H, NCH3), 5.95 (t, 3J ϭ 7.2 Hz, 1 H, CH), No. reflect. measured 13711
4
3
3
No. unique data
Parameters
4834 (Rint ϭ 0.0367) 2535 (Rint ϭ 0.0222)
6.12 (dd, JP,H ϭ 5.0, J ϭ 8.5 Hz, 1 H, CH), 6.86 (dt, J ϭ 8.1,
4J ϭ 1.5 Hz, 1 H, CH), 7.22 (dt, J ϭ 7.4, J ϭ 1.5 Hz, 1 H, CH),
7.21Ϫ7.29 (m, 3 H, CH), 7.59Ϫ7.67 (m, 2 H, CH); cis-9 (21%):
δ ϭ Ϫ0.07 (dd, trans3JP,H ϭ 4.2 Hz, cis3JP,H ϭ 8.2 Hz, 3 H, NiCH3),
3
4
541
292
GoF on F2
1.172
0.0727
0.3110
1.163
0.0389
0.1295
R1 [I Ն 2σ(I)]
wR2 (all data)
2
2
1.12 (d, JP,H ϭ 4.8 Hz, 9 H, PCH3), 1.47 (d, JP,H ϭ 13.2 Hz, 9
H, PCH3), 2.59 (s, 3 H, NCH3), 5.83 (t, 3J ϭ 7.1 Hz, 1 H, CH),
4
3
3
6.17 (dd, JP,H ϭ 5.2, J ϭ 8.2 Hz, 1 H, CH), 6.41 (dt, J ϭ 8.8,
4J ϭ 1.5 Hz, 1 H, CH), 6.86 (dt, J ϭ 8.1, J ϭ 1.5 Hz, 1 H, CH),
3
4
Acknowledgments
Financial support of this work by the Fonds der Chemischen Indu-
strie is gratefully acknowledged.
7.31Ϫ7.33 (m, 3 H, CH), 7.70Ϫ7.80 (m, 2 H, CH) ppm. 13C NMR
2
(75.4 MHz, [D8]THF, 296 K): trans-9: δ ϭ Ϫ14.4 (d, JP,C
14.5 Hz, NiCH3), 16.3 (d, JP,C ϭ 6.9 Hz, PCH3), 29.1 (d, JP,C
ϭ
2
1
ϭ
2
5.8 Hz, CCH3), 36.3 (d, JP,C ϭ 11.9 Hz, CCH3), 44.6 (s, NCH3),
107.5 (s, C-2), 110.1 (s, C-5), 110.7 (d, 2JP,C ϭ 10.8 Hz, o-C), 127.9
3
[1]
[1a] C. W. G. Ansell, M. McPartlin, P. A. Tasker, M. K. Cooper,
(s, C-3), 128.5 (d, JP,C ϭ 6.8 Hz, p-C), 131.8 (s, C-4), 132.8 (d,
3JP,C ϭ 8.4 Hz, m-C), 133.9 (s, i-C), 134.8 (s, C-6), 170.5 (m, NC-
1) ppm. 31P NMR (81 MHz, [D8]THF, 233 K): trans-9 (79%): δ ϭ
[1b]
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